Chromed monoazo compound



Patented Dec. 14., 1948 UNITED mess PATENT OFFICE 2,456,230 l CHROMED MONOAZQCQMBOUND I Willy Widmer, Bottmingen, Switzerland, assignor to Ciba Limited, a Swiss firm No Drawing. Application March 9, 1945, Serial No; 581,966. In Switzerland December 2, 1943 Section 1, Public Law 690, August 8, 1946 j Patent 'e rpires December 2, 1963 The present invention is concerned with complex metal compounds of azo-dyestufis containing ortho-amino-ortho-hydroxy-ace-grouping.

an More particularly the present invention is con cerned' with complex metal compounds of azo dyestufis-obtained by coupling anortho-hydroxy diazo compound-with a substitutedZ-aminonaphthalene as defined below. j

'It has previously been proposed to treat orthohydroxy-azo-dyestufis obtained from 2-arnin'onaphthalenes as coupling components with agents yielding metal, especially with agents yielding chromium. Although some valuable complex chromium compounds have been ob-' tained' in this way the known dyestufis of this kind are still defective in somerespects, such as Furthermore some attractive purity of shade. shades of green especially on the yellowish side, could not be obtained therewith.

It is an object of the present invention to provide improved dyestufis of the aforementioned type. Further objects will appear as the specification proceeds.

It has now. been found that valuable azo-dyestuffs may be produced if ortho-hydroxy-diazo compounds are united with such Z-aminonaphthalenes capable .of. coupling in,,the l position as fo'r in s ta'nce of alcohol, pyridine or sodium acefibers. Acidv wool dyestuffs inparticular are I which contain at least oneetherlfiedhydroxyl group and, if necessary, treating the dyestufis thus obtained with agents yielding metal.

Ortho-hydroxy diazo compounds which come especially into consideration'for the presentprocess are diazotized z-amino-l-phenols. These may contain further substituents, such as halogens, alkyl groups and nitro groups, and especially also sulfonlc acid groups. As examples theremay. be mentioned 6-- or 5-nitro-2-amino-lephenolsel-. sulfonic acid, 4-.-nitro-2-amino-l-phenolli sule fonic acid and 2-amino-1-phenol-4:6-disulfonic acid.

The diazotiz'ation of these products is. efiected in known manner. The v2-aminonaphtha lenes containing at least one etherified hydroxyl I group which serve as azo components in the present process may contain jthe-etherified hydroxyl groupfor instance in the benzene nucleus which is removed from the amino'group and preferably.

also in the ,B-position, particularly in the '6- position; The fiaposition appears to possess a particular importance, but'the invention is not limited to this particular case. Theether group 4 Claims. (Cl. 260-151) for-example Z-amino-G-methoxyand -6-ethoxynaphthalene, as well as glycerine-mono- (2-amino-fi-naphthyl) -ether.

The coupling in ortho-position to the amino group may be effected in a manner-known in itself, for example in an acid, preferably*weakly acid medium: In many cases'thecoupling may be accelerated byadditions'of various kinds, such tate.

The dyestufls thus ,obtained may serve for the dyeingvand printing of the most various materials lsuch as plastic masses, lacquers, textile obtained if care beftaken in'the choice of the components, so that at least one of the components used for the synthesis of the dyestufis contains an acid solubilizing group, such as a sulfonic acid group.

Particularly valuable dyestuffs are obtained by causin agents yielding metal to react with the products obtained according to the above particulars, the metals having-to be chosen according to the intended purpose of application. For the productionof metalliierous acid'wool dyestuffs use is preferably made of agents yielding chromium, particularly those which contain the chromium 111a trivalent form and. do not thereforeexert' a detrimental oxidizing action. The treatment withchromium (III) compounds may be'eiiected in a manner known-in itself, in an acid, neutral or alkaline mediumfwith or Without addition of, for example, neutral salts, if

' necessaryof a complex-forming nature, organic solvents, such as alcohol or pyridine, in an open vessel or under pressure. The complex metal andin particular chromium compounds of the presentfdyestuffs thus obtained serve with advantage for the dyeing and printing of animal fibers, such as leather, silk, and principally wool according to methods known per se.

According to the present process, dyestufis, among others, may be obtained which dye wool in pure, especially yellowish green shades of good fastness properties and possessing a pleasing shade in artificial light.

The following examples illustrate the invention, the parts being by"'weight-:-

Example 1 23.4 parts of 6-nitro-2-amino-l-phenoll-sul fonic acid are diazotized in known manner and coupled with 18 parts of 2-aminG 'G metI'idXy naphthalene in presence of acct-101 acid or alcohola- The filtered dyestufi of the formula S0311 OCHs isldi ssolvecl iri' mocpa'rts or wateratbbilin t m perature and mixed with a solution-or chromium formiate Containing a uantity of chromium corresponding to 814" parts -of' chrcfmium oxide. The Whole heated under renuxrbr some t'iffi at the boil'g' and the chromium compound trims:

olotaineld j which is sparingly soluble water is filt n. By issolving; it i'r r dilute I caustic d 91Pfi W enn ieitme l i e i i soluble form-1 Aftertdryi'nglit}forms a grey-mack" powder; hichdissolve'sqm Water and clilute sd diumcarbonate solution to a greyish green somnon-, and in concentrated: sulfuric acid to 'a'i red-brown solution. The dyestufi? dyeswooffrorn a,sulturic* acid loath uniform, pure; yellowish green tints which have agood fastne s's to light qr g? a .t n. W i A similar; dyestufi is obtained if glycerinecomponent in place" 0t 2-amino -6 -methoxynaph thalene.

ence or pyridinef The dyestuff or theformula temperature in 180i) partsof water' and mixed" Witha solution of chromiu-m'formiate' which- @6125 tains aquantit'y of chromium corresponding "to-' 8 parts of chromium oxide. The-whole is heated for some time at the boil under" refluii, and the v chromiuincompound thus ohta'ine'd} w'hi'chf is" sparingly soluble in water, isfilt'ered ofi; B'y' dissolving it' in dilute caustic sodasolution it is transformed into an easily soluble ramp and forms after dryinga; blackish owder dis solves in water and dilute sodium carbonate solution to a greyreen andmco eentr ee'su furic acid to" a BbrdeauX r'ed' solution. The dye 4 green tints which have a good fastness to fulling and to light.

Example 3 26.9 parts of 2-amino-1-phen0l-4:G-disulfonic acid are diazotized in a concentrated solution and coupled with 18 parts of 2-amino-6-methoxynaphthalene in the presence of pyridine acetate. The filtered dyestufi of the formula bathpure yellowishgreenand uniform" tints whichhaveagoodfastness to light'and; to tullinge A similar dyestuff is obtained-if 2'-amino-6- ethoxy-napthalene is' used as the an component ionic aci'd ar'e diazo'tiz edin; known manner, and

coupled with 1 8' parts 'of 2-amino-6P nethoXyfiltered oif dyes'tuffof the formula is dis wee-at; boiling temperature in moo-parts of water; and miseowith chromium" rormiate solution will Y cories'pondiri I to"- a', parts or" chromium" oxide;

furic' 'giciq Bat ipage; green ti'r' ts' whim-have a good fastriess tofulling andFto-light.

Emmpze *5 70 iic'o'f parts er'wen'" wetted'w'ab are introduced at s o crm to a'dye'batn" of 3600 parts 'o'fw ate'r which contains 4p acid, rd parts of c "'s'talliie'd'sbdiuni sulfate and H depart dfitlfhfioiiiilifii compound obtained a'c-' cording tdE-Siaiiiifile 1'; The temperature is then in plaee of the2 amino=6-methoxy-naphthalena naphthalene in the pres'e 'ice of pyridine. Theont'ains a quantity or chromium" raised within one hour to the boil, whereupon a OH further 4 parts of concentrated sulfuric acid are added, dyeing being then continued at the boil for N=N 1% hours. The wool is then rinsed and finished as usual. It is dyed pure yellowish green. 5 H:N

What I claim is:

1. A complex chromium compound of a mono- S031; @0113 azo dyestuif of the general formula 151038 4. A complex chromium compound of the dye- 10 stufi of the formula VV'ILLY WIDMER.

HsC-O REFERENCES CITED wherein :2: stands for a member selected from the The following references are of record in the group consisting of -SO3H and NO2.

2. A complex chromium compound of the dyefile of this Patent: 7 stuff of the formula UNITED STATES PATENTS 0H Number Name Date 421,640 Weinberg Feb. 18, 1890 N0,- N=N 1,835,821 Straub Dec. 8, 1931 2,053,818 Felix et a1 Sept. 8, 1936 H2N 39 2,090,432 Straub -et a] Aug. 17, 1937 SOQH 00m FOREIGN PATENTS v Number Country Date 3. A complex chromium compound of the dye- 500,075 Great Britain Feb. 2, 1939 stuff of the formula 793,459 France Nov. 23, 1935 

